EP4097387A1 - Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff - Google Patents

Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff

Info

Publication number
EP4097387A1
EP4097387A1 EP21708270.0A EP21708270A EP4097387A1 EP 4097387 A1 EP4097387 A1 EP 4097387A1 EP 21708270 A EP21708270 A EP 21708270A EP 4097387 A1 EP4097387 A1 EP 4097387A1
Authority
EP
European Patent Office
Prior art keywords
weight
layer
composition
polymer
multilayer structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21708270.0A
Other languages
English (en)
French (fr)
Inventor
Nicolas Dufaure
Patrick Dang
Antoine GOUPIL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4097387A1 publication Critical patent/EP4097387A1/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/58—Winding and joining, e.g. winding spirally helically
    • B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
    • B29C53/602—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels for tubular articles having closed or nearly closed ends, e.g. vessels, tanks, containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/58—Winding and joining, e.g. winding spirally helically
    • B29C53/581—Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material
    • B29C53/582—Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material comprising reinforcements, e.g. wires, threads
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C63/0017—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor characterised by the choice of the material
    • B29C63/0021—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor characterised by the choice of the material with coherent impregnated reinforcing layers
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0604—Liners
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0614—Single wall
    • F17C2203/0619—Single wall with two layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/066—Plastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0663—Synthetics in form of fibers or filaments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0675—Synthetics with details of composition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/01—Pure fluids
    • F17C2221/012—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0107—Single phase
    • F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
    • F17C2223/036—Very high pressure (>80 bar)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2270/00—Applications
    • F17C2270/01—Applications for fluid transport or storage
    • F17C2270/0165—Applications for fluid transport or storage on the road
    • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

Definitions

  • TITLE MULTI-LAYER STRUCTURE FOR THE TRANSPORT OR STORAGE OF
  • the present patent application relates to composite multilayer structures for the transport, distribution or storage of hydrogen, in particular for the distribution or storage of hydrogen, and their manufacturing process.
  • Hydrogen tanks are a subject that is currently attracting a lot of interest from many manufacturers, especially in the automotive field.
  • One of the goals is to offer vehicles that pollute less and less.
  • electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles.
  • thermal vehicles such as gasoline or diesel vehicles.
  • the battery is a relatively complex component of the vehicle.
  • the electric vehicle still suffers today from several problems, namely the autonomy of the battery, the use in these rare earth batteries whose resources are not inexhaustible, recharging times much longer than the durations. tank filling, as well as a problem of electricity production in the different countries to be able to recharge the batteries.
  • Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.
  • Hydrogen tanks generally consist of a metal casing (liner or sealing layer) which must prevent the permeation of hydrogen.
  • liner or sealing layer One of the types of tanks being considered, called Type IV, is based on a thermoplastic liner around which a composite is wrapped.
  • thermoplastic resin liner or sealing sheath
  • a reinforcing structure made up of fibers (glass, aramid, carbon). called sheath or reinforcing layer which allow to work at much higher pressures while reducing the mass and avoiding the risk of explosive rupture in the event of severe external attacks.
  • the permeability of the liner is indeed a key factor in limiting hydrogen losses from the tank;
  • the first generation of type IV tanks used a liner based on high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • HDPE has the drawback of having too low a melting temperature and high hydrogen permeability, which is a problem with the new thermal withstand requirements and does not allow the filling speed of the tank to be increased. tank.
  • PA6 polyamide
  • International application WO 2016/166326 describes a method of manufacturing an internal shell of a type IV composite tank delimiting an internal cavity intended to receive a pressurized fluid and comprising at least one metal base, and a subsequent step of depositing, on the outer surface of the inner shell, a fibrous material to form the outer shell of the reservoir.
  • thermoplastic material being a material chosen from the group consisting of a modified nylon 6 and nylon 11.
  • French application FR2923575 describes a reservoir for storing fluid under high pressure comprising at each of its ends along its axis a nozzle metal end, a liner enveloping said end caps and a structural layer of fiber impregnated with thermosetting resin enveloping said liner.
  • the matrix of the composite in order to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, in order to optimize its processing temperature.
  • the possible modification of the composition of the material composing the sealing sheath, which will be made, must not result in a significant increase in the manufacturing temperature (extrusion-blow molding, injection, rotomoulding, etc.) of this liner, compared to what is practiced today.
  • the present invention therefore relates to a multilayer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, a sealing layer (1) and at least one composite reinforcing layer.
  • thermoplastic polyamide PA11 polymer comprising a limited proportion of impact modifier and plasticizer, for the sealing layer, with a different polymer for the matrix of the composite and in particular a epoxy resin or epoxy-based, wound on the waterproofing layer, made it possible to obtain a structure suitable for the transport, distribution or storage of hydrogen and in particular an increase in the maximum temperature of use up to 120 ° C, thus increasing the tank filling speed.
  • thermoplastic polymer PA11 (or polyamide 11) is marketed by the company Arkema and is obtained in particular from the polycondensation of 11-amino undecanoic acid.
  • multilayer structure is meant a tank comprising or made up of several layers, namely a waterproofing layer and several reinforcing layers, or a waterproofing layer and a reinforcing layer.
  • the multilayer structure is therefore meant to the exclusion of a pipe or tube.
  • Poly ether block amide are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY unit obtained from polycondensation:
  • diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and
  • dicarboxylic acid being preferably chosen from: a linear or branched aliphatic dicacid, or a mixture of these, said diamine and said dicacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.
  • Nucleating agents are known to those skilled in the art and refer to a substance which, when incorporated into a polymer, forms nuclei for crystal growth in the molten polymer.
  • They can be chosen, for example, from micro talc, carbon black, silica, titanium dioxide and nanoclays.
  • PA6 is excluded from said composition.
  • said multilayer structure consists of two layers, a sealing layer and a reinforcing layer.
  • the waterproofing layer is the innermost layer relative to the composite reinforcement layers which are the outermost layers.
  • the tank can be a tank for the mobile storage of hydrogen, i.e. on a truck for the transport of hydrogen, on a car for the transport of hydrogen and the supply of hydrogen d '' a fuel cell for example, on a train for the supply of hydrogen or on a drone for the supply of hydrogen, but it can also be a stationary storage tank for hydrogen in a station for the distribution of hydrogen to vehicles.
  • the sealing layer (1) is impermeable to hydrogen at 23 ° C, that is to say that the permeability to hydrogen at 23 ° C is less than 500 cc.mm/m2. 24h. .atm at 23 ° C under 0% relative humidity (RH).
  • the composite reinforcing layer (s) is (are) wound (s) around the waterproofing layer by means of tapes (or tapes or rovings) of fibers impregnated with polymer which are deposited, for example, by filament winding.
  • the polymers are different.
  • the polymers of the reinforcing layers are identical, there may be several layers present, but advantageously, only one reinforcing layer is present and which then has at least one complete winding around the waterproofing layer.
  • the other composite reinforcement layers may or may not also adhere to each other.
  • a waterproofing layer and a reinforcing layer are present and do not adhere to each other.
  • a sealing layer made of PA11 and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition. mainly comprising at least one polymer P2j, in particular an epoxy resin or an epoxy-based resin.
  • a waterproofing layer and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising a P2j polymer which is an epoxy or epoxy-based resin.
  • epoxy-based throughout the description means that the epoxy represents at least 50% by weight of the matrix.
  • the waterproofing layer consists of a composition comprising predominantly at least one thermoplastic polymer PA11.
  • said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix.
  • said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight 90% by weight, relative to the total weight of the composition and the matrix.
  • Said composition can also comprise impact modifiers of up to 15% by weight relative to the total weight of the composition and / or a plasticizer and / or additives.
  • the additives can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, with the exception of a nucleating agent, in particular the additives are chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, except for a nucleating agent.
  • Said other polymer can be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (Ethylene vinyl alcohol).
  • EVOH Ethylene vinyl alcohol
  • said composition comprises mainly said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of 'additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight. weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises mainly said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and 0.1 at 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight relative to the total weight of the composition.
  • said composition is devoid of impact modifier.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100 %.
  • said composition therefore comprises said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition is devoid of plasticizer.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% in weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition therefore comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists predominantly of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives. , the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition is devoid of impact modifier and plasticizer.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition therefore comprises said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises an impact modifier of 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight, in particular from 5 to 12% by weight of impact modifier and said composition is devoid of plasticizer relative to the total weight of the composition.
  • said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight and from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition.
  • the number-average molecular mass Mn of said thermoplastic polyamide PA11 polymer is preferably in a range going from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to standard ISO 307: 2007 but by changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
  • Polyamide PA11 is a homopolyamide but it would not be departing from the scope of the invention if the constituent composition of the waterproofing layer included a copolyamide based on PA11 in which the PA11 unit is predominant, that is to say greater than 50% by weight, in particular greater than 60% by weight, greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, relative to the total of the units of said copolyamide or a mixture thereof .
  • the polyamide PA11 is a homopolyamide.
  • the impact modifier can be any impact modifier from the moment when a polymer of lower modulus than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.
  • the impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and of Tg less than 0 ° C (measured according to the 11357-2 standard at the inflection point of the DSC thermogram ), in particular a polyolefin.
  • PEBAs are excluded from the definition of impact modifiers.
  • the polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
  • polystyrene resin For simplicity, the polyolefin has been designated by (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) have been described below.
  • An unfunctionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene, or linear low density polyethylene
  • VLDPE very low density polyethylene, or very low density polyethylene
  • metallocene polyethylene metallocene polyethylene
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
  • EPR abbreviation of ethylene-propylene-rubber
  • EPDM ethylene / propylene / diene
  • SEBS ethylene-butene / styrene
  • SBS styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • the functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride or epoxy functions.
  • polyolefins (B2) grafted or co- or ter polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the latter being able to be totally or partially neutralized by metals such as Zn, etc.) or alternatively by carboxylic acid anhydrides such as maleic anhydride.
  • a functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting, for example from 0.01 to 5% by weight.
  • the functionalized polyolefin (B1) can be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:
  • - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
  • EPR abbreviation of ethylene-propylene-rubber
  • EPDM ethylene / propylene / diene
  • SEBS ethylene-butene / styrene
  • SBS styrene / butadiene / styrene
  • SIS isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate;
  • the functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride then condensed with mono-amine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
  • the functionalized polyolefin (B1) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
  • (meth) acrylic acid can be salified with Zn or Li.
  • alkyl (meth) acrylate in (B1) or (B2) denotes methacrylates and acrylates of C1 to C8 alkyl, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
  • the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.
  • a difunctional reagent such as as diacid, dianhydride, diepoxy, etc.
  • copolymers mentioned above, (B1) and (B2) can be copolymerized in a random or block fashion and have a linear or branched structure.
  • the molecular weight, the MFI number, the density of these polyolefins can also vary to a large extent, which will be appreciated by those skilled in the art.
  • MFI short for Melt Flow Index, is the melt flow index. It is measured according to standard ASTM 1238.
  • the unfunctionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-Pentene.
  • PPs high density PE, medium density PE, linear low density PE, low density PE, very low density PE.
  • polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.
  • the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units bearing polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
  • polymers mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader® from the Applicant or polyolefins grafted with l.
  • maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, of alkyl acrylate and of (meth) acrylic acid.
  • Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or mono-amino polyamide oligomers.
  • said constituent composition of said sealant layer or layers is devoid of polyether block amide (PEBA).
  • PEBAs are therefore excluded from the impact modifiers.
  • said transparent composition is devoid of core-shell particles or “core-shell” core-shell polymers.
  • core-shell particle it is necessary to understand a particle of which the first layer forms the core and the second or all of the following layers form the respective shell.
  • the core-shell particle can be obtained by a multi-step process comprising at least two steps. Such a method is described for example in documents US2009 / 0149600 or EP0722961. Regarding the plasticizer
  • the plasticizer can be a plasticizer commonly used in compositions based on polyamide (s).
  • a plasticizer which has good thermal stability so that no fumes are formed during the stages of mixing the various polymers and of processing the composition obtained.
  • this plasticizer can be chosen from: benzene sulfonamide derivatives such as n-butyl benzene sulfonamide (BBSA), ortho and para isomers of ethyl toluene sulfonamide (ETSA), N-cyclohexyl toluene sulfonamide and N- (2-hydroxypropyl) benzenesulfonamide (HP-BSA), esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
  • BBSA n-butyl benzene sulfonamide
  • ETSA ethyl toluene sulfonamide
  • HP-BSA N- (2-hydroxypropyl) benzenesulfonamide
  • esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
  • EHPB 2-decylhexyl para-hydroxybenzoate
  • HDPB 2-decylhexyl para-hydroxybenzoate
  • esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol
  • esters of citric acid or hydroxymalonic acid such as oligoethylene oxymalonate.
  • a preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
  • Another more particularly preferred plasticizer is N- (2-hydroxy-propyl) benzene sulfonamide (HP-BSA).
  • HP-BSA N- (2-hydroxy-propyl) benzene sulfonamide
  • the polymer P2j can be a thermoplastic polymer or a thermosetting polymer.
  • One or more composite reinforcement layers may or may be present.
  • the term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix of the composite.
  • said at least one major polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight, relative to the weight total composition
  • Said composition can also comprise impact modifiers and / or additives.
  • the additives can be selected from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a plasticizer and a colorant, except for a nucleating agent.
  • said composition consists of said thermoplastic polymer P2j predominantly, from 0 to 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of constituents of the composition being equal to 100% by weight.
  • Said at least one majority polymer of each layer may be identical or different.
  • a single major polymer is present at least in the composite reinforcing layer and which does not adhere to the waterproofing layer.
  • each reinforcing layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin.
  • thermoplastic or thermoplastic polymer
  • Tg temperature of glass transition
  • Tf melting temperature
  • Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
  • the number average molecular weight Mn of said thermoplastic polymer is preferably in a range of 10,000 to 40,000, preferably 10,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to ISO 307: 2007 but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
  • polyamides in particular comprising an aromatic and / or cycloaliphatic structure
  • copolymers for example polyamide-polyethers, polyesters, copolymers, polyaryletherketones (PAEK), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides (in particular PSU )sulfones, polylsulfones polyarylsulfones such as polyphenyl sulfones
  • PAEK polyaryletherketones
  • PEEK polyetherether ketones
  • PEKK polyetherketone ketones
  • PEKEKK polyetherketoneetherketone ketones
  • PEI polyetherimides
  • PSU polyamide-imides
  • PPSU polyethersulfones
  • semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.
  • the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
  • the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca).
  • (Cb diacid) with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids ;
  • XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 5T, A / 6T, A / 9T, A / 10T or A / 11 T, A being as defined above, in particular a polyamide chosen from a PA MPMDT / 6T, one PA11 / 10T, one PA 5T / 10T, one PA 11 / BACT, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 10T, PA 11 / B
  • T corresponds to terephthalic acid
  • MXD corresponds to m-xylylenediamine
  • MPMD corresponds to methylpentamethylene diamine
  • BAC corresponds to bis (aminomethyl) cyclohexane.
  • Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80 ° C.
  • thermosetting polymers are chosen from epoxy or epoxy-based resins, polyesters, vinyl esters and polyurethanes, or a mixture of these, in particular epoxy or epoxy-based resins.
  • each composite reinforcing layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin.
  • Said composition comprising said polymer P2j may be transparent to radiation suitable for welding.
  • the winding of the composite reinforcing layer around the waterproofing layer is carried out in the absence of any subsequent welding.
  • Said multilayer structure therefore comprises a waterproofing layer and at least one composite reinforcing layer which is wrapped around the waterproofing layer and which may or may not adhere to each other.
  • sealing and reinforcing layers do not adhere to each other and consist of compositions which respectively comprise different polymers.
  • said different polymers can be of the same type.
  • the waterproofing layer consisting of a composition comprising an aliphatic polyamide PA11
  • the reinforcing layer (s) is (are) or consists of a composition comprising a polyamide which is not aliphatic and which is by example a semi-aromatic polyamide so as to have a high tg polymer as the matrix of the composite reinforcement.
  • Said multilayer structure can include up to 10 composite reinforcement layers of different types.
  • said multilayer structure comprises a sealing layer and one, two, three, four, five, six, seven, eight, nine or ten layers of composite reinforcement.
  • said multilayer structure comprises a waterproofing layer and one, two, three, four or five composite reinforcement layers.
  • said multilayer structure comprises a waterproofing layer and one two or three composite reinforcement layers.
  • compositions which respectively comprise different polymers consist of compositions which respectively comprise polyamides corresponding to polyamides PA11 and an epoxy resin or epoxy resin P2j.
  • said multilayer structure comprises a single waterproofing layer and several reinforcing layers, said adjacent reinforcing layer being wrapped around said waterproofing layer and the other reinforcing layers being wrapped around the reinforcing layer. directly adjacent.
  • said multilayer structure comprises a single waterproofing layer and a single composite reinforcing layer, said reinforcing layer being wrapped around said waterproofing layer.
  • each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin.
  • the P2j polyamide is identical for all the reinforcing layers.
  • the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy resin. or epoxy based.
  • the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, said polymer P2j being a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / BACT, a PA 5T / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and a PA 11 / MXDT / 10T.
  • said multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA11 / 10T, one PA 11 / BACT, one PA 5T / 10T, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and one PA 11 / MXDT / 10T.
  • the multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is an epoxy or epoxy-based resin.
  • said multilayer structure further comprises at least one outer layer made of a continuous fiberglass fibrous material impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
  • Said outer layer is a second but transparent reinforcing layer which makes it possible to put an inscription on the structure.
  • Said outer layer in no way corresponds to the layer located above the outermost composite reinforcing layer of polyamide polymer, the structure of which is not mentioned above.
  • constituent fibers of said fibrous material they are in particular fibers of mineral, organic or plant origin.
  • said fibrous material can be sized or not sized.
  • Said fibrous material can therefore comprise up to 3.5% by weight of an organic material (thermosetting or thermoplastic resin type) called sizing.
  • fibers of mineral origin mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers, for example.
  • fibers of organic origin mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example.
  • they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or greater than the Tm of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
  • they are based on a semi-crystalline thermoplastic polymer and have a melting point Tm greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is amorphous, or greater than the Tm. of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
  • the organic fibers constituting the fibrous material during impregnation with the thermoplastic matrix of the final composite.
  • the fibers of plant origin mention may be made of natural fibers with base of flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulose fibers, in particular viscose. These fibers of plant origin can be used pure, treated or else coated with a coating layer, with a view to facilitating the adhesion and the impregnation of the thermoplastic polymer matrix.
  • the fibrous material can also be fabric, braided or woven with fibers.
  • organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and to form the pre-impregnated fibrous material.
  • the rovings of organic fibers can have several grammages. They can also have several geometries.
  • the fibers constituting the fibrous material can also be in the form of a mixture of these reinforcing fibers of different geometries. Fibers are continuous fibers.
  • the fibrous material is chosen from glass fibers, carbon fibers, basalt or basalt-based fibers, or a mixture of these, in particular carbon fibers.
  • It is used as a wick or several wicks.
  • the present invention relates to a method of manufacturing a multilayer structure as defined above, characterized in that it comprises a step of preparing the sealing layer by extrusion blow molding, by rotational molding, by injection and / or extrusion.
  • said method of manufacturing a multilayer structure comprises a step of filament winding of the reinforcing layer as defined above around the sealing layer as defined above.
  • Figure 1 shows the notched Charpy impact at -40 ° C according to ISO 179-1: 2010 of four liners: from left to right PA11, PA12, PA6 and PA66.
  • Figure 2 shows the hydrogen permeability at 23 ° C of PA12 and HDPE liners.
  • the permeability must then be multiplied by 101325.
  • Figure 3 shows the notched Charpy shock at -40 ° C according to ISO 179-1: 2010 for PA11 and PA12 liners: for each group of histograms, PA11 is on the left and PA12 is on the right.
  • the first group corresponds to 0% plasticizer, the second group to 7% plasticizer and the last group to 12% plasticizer.
  • the tanks are obtained by rotational molding of the sealing layer (liner) at a temperature suited to the nature of the thermoplastic resin used.
  • a wet filament winding process is then used which consists in winding fibers around the liner, which fibers are pre-impregnated in an epoxy bath. liquid or a liquid epoxy-based bath. The reservoir is then polymerized in an oven for 2 hours.
  • thermoplastic resin a fibrous material impregnated with the thermoplastic resin (tape) is used.
  • This tape is deposited by filament winding using a robot comprising a 1500W power laser heater at a speed of 12m / min and there is no polymerization step.
  • Example 1 Notched Charpy shock at -40 ° C according to ISO 179-1: 2010
  • Two long chain liners of PA11 and PA12 and two short chain liners were prepared by rotational molding as above.
  • the cold resistance of the PA1 liner is very much better than that of the long chain liner PA12 and the short chain liners PA6 and PA66.
  • Two long chain liners one in PA11 (Arkema) and the second in PA12 (Arkema) and one liner in HDPE were prepared by rotational molding and the hydrogen permeability at 23 ° C was tested.
  • Example 3 influence of the proportion of plasticizer (N-butyl benzene sulfonamide: BBSA) on the notched Charpy impact at -40 ° C according to ISO 179-1: 2010
  • Two liners PA11 and PA12 without plasticizer or comprising 7 or 12% plasticizer (BBSA) relative to the total weight of the composition were prepared by rotational molding.
  • LT cocktail having the following composition: lotader® 4700 (50%) + lotader® AX8900 (25%) + lucalene® 3110 (25%)) on the liner's hydrogen permeability PA11.
  • the permeability can also be expressed in (cc.25p / m 2 .24h.Pa). The permeability must then be multiplied by 101325. The results show that the proportion of impact modifier influences the permeability to hydrogen.
  • Type IV hydrogen storage tank composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and a waterproofing layer of PA11.
  • the operating temperature is sufficient for rapid filling of the tank, especially in 3 to 5 minutes.
  • Type IV hydrogen storage tank composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and an HDPE waterproofing layer.
  • the operating temperature is too low for rapid filling of the tank, especially in 3 to 5 minutes.
  • Example 7 Type IV hydrogen storage tank, composed of a reinforcement of BACT / 10T carbon fiber T700SC31 E composite (produced by Toray) and a waterproofing layer of PA11.
  • the BACT / 10T type composition chosen has a melting point, Tm, of 283 ° C, a crystallization temperature, Te, of 250 ° C and a glass transition temperature of 164 ° C.
  • Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
  • a PA BACT / 10T-based composite exhibits a high Tg matrix, but without having long crosslinking, of the 8h type at 140 ° C.

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EP21708270.0A 2020-01-28 2021-01-26 Mehrschichtstruktur zum transport oder zur speicherung von wasserstoff Pending EP4097387A1 (de)

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FR2000815A FR3106525B1 (fr) 2020-01-28 2020-01-28 Structure multicouche pour le transport ou le stockage de l’hydrogene
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FR2629090B1 (fr) 1988-03-24 1990-11-23 Atochem Copolymere greffe a base d'alpha-mono-olefine, son procede de fabrication, son application a la fabrication d'alliages thermoplastiques, alliages thermoplastiques obtenus
US5499739A (en) * 1994-01-19 1996-03-19 Atlantic Research Corporation Thermoplastic liner for and method of overwrapping high pressure vessels
US5534594A (en) 1994-12-05 1996-07-09 Rohm And Haas Company Preparation of butadiene-based impact modifiers
FR2858626B1 (fr) 2003-08-05 2005-10-07 Atofina Polyamides semi aromatiques souple a faible reprise en humidite
DE602005022494D1 (de) 2004-11-22 2010-09-02 Arkema Inc Schlagzäh modifizierte thermoplastische harzzusammensetzung
FR2902364B1 (fr) * 2006-06-16 2012-04-27 Commissariat Energie Atomique Procede de fabrication d'une vessie d'etancheite en polymere thermodurcissable pour un reservoir contenant un fluide sous pression, tel qu'un reservoir composite, et reservoir
FR2923575A1 (fr) * 2007-11-13 2009-05-15 Michelin Soc Tech Reservoir de fluide sous pression, methode et appareil pour la fabrication d'un tel reservoir.
US20110039470A1 (en) * 2009-07-30 2011-02-17 E.I. Du Pont De Nemours And Company Overmolded heat resistant polyamide composite structures and processes for their preparation
CN103148340B (zh) * 2013-04-01 2015-07-01 北京京城机电控股有限责任公司装备技术研究院 一种钢丝缠绕结构的高压气瓶
EP3069873B1 (de) * 2015-03-17 2017-09-06 Evonik Degussa GmbH Mehrschichtverbund mit schichten aus teilaromatischen polyamiden
FR3035173B1 (fr) * 2015-04-15 2017-12-15 Commissariat Energie Atomique Procede de preparation de la coque interne d'un reservoir composite de type iv pour le stockage de fluide sous pression
DE102016120893A1 (de) * 2016-11-02 2018-05-03 Rehau Ag + Co Verfahren zur Herstellung eines Druckspeichers
CN110325777A (zh) 2017-02-24 2019-10-11 株式会社普利司通 氢气输送部件

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KR20220135239A (ko) 2022-10-06
CN115053094A (zh) 2022-09-13
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FR3106525A1 (fr) 2021-07-30

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